CN101671448A - Amphiphilic coupling agent and preparation method thereof - Google Patents
Amphiphilic coupling agent and preparation method thereof Download PDFInfo
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- CN101671448A CN101671448A CN200910190899A CN200910190899A CN101671448A CN 101671448 A CN101671448 A CN 101671448A CN 200910190899 A CN200910190899 A CN 200910190899A CN 200910190899 A CN200910190899 A CN 200910190899A CN 101671448 A CN101671448 A CN 101671448A
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Abstract
The invention discloses an amphiphilic coupling agent and a preparation method thereof, and the amphiphilic coupling agent comprises the following components by weight percent: 25-30% of aluminate coupling agent, 34-38% of fatty acid and 9-14% of surfactant. The amphiphilic coupling agent is characterized in that the amphiphilic coupling agent can directly modify a powder body with high water content or high hydroxyl content and do not need to carry out the strict drying treatment before modifying the powder body, thereby simplifying the production technology of simplifying the powder body, shortening the technological process, saving the investment, saving the manpower and the energy consumption, reducing the production cost, reducing the environmental pollution and being applicable to dry or wet modification of inorganic powder bodies (such as heavy calcium carbonate, light calcium carbonate, talc powder, wollastonite, barite, kaolin and the like) and organic powder bodies (such as wood powder, starch and the like). The preparation method is simple and applicable to the industrial large-scale production.
Description
Technical field
The present invention relates to a kind of auxiliary chemicals, particularly a kind of amphiphilic coupling agent also relates to the preparation method of this amphiphilic coupling agent.
Background technology
Thermoplastics inorganic or that organic powder is filling-modified is a kind of important matrix material, and purposes is widely arranged.Consistency and interface bonding state that an important factor that determines this composite property is powder and resin matrix.For improving the consistency between powder and the resin matrix, usually adopt traditional coupling agent such as titanate coupling agent, aluminate coupling agent and silane coupling agent etc. carry out surface modification to powder, all there are the following problems but traditional coupling agent is when using: (a large amount of hydroxyls can form intermolecular hydrogen bonding or intramolecular hydrogen bond when higher or hydroxy radical content was higher when the powder water content, has water-absorbent, rate of moisture absorption can reach 8%～12%), hydrolysis can take place in coupling agent gradually, thereby make the consistency variation between modified powder and the resin matrix, cause derived product bubble to occur, scratches, defects such as brilliant point, even the serious downslide of physical indexs such as physical strength appears.Carry out modification and earlier powder is dried again after processing makes its water content reduce to below 0.5%, technical process is prolonged, energy consumption increases.
Summary of the invention
In view of this, for solving traditional coupling agent to a high-moisture or the unfavorable difficult problem of the powder-modified effect of high hydroxyl content, one of purpose of the present invention is to provide a kind of amphiphilic coupling agent, has the characteristics of direct modification high-moisture or high hydroxyl content powder, need not before modification powder to be carried out harsh oven dry and handles, can simplify powder-modified production technique, shortened process is saved investment, saves manpower and energy consumption, reduce production costs, reduce environmental pollution.Two of purpose of the present invention is to provide a kind of preparation method of described amphiphilic coupling agent, and is easy and simple to handle, is fit to large-scale industrialization production.
For achieving the above object, the present invention adopts following technical scheme:
1, amphiphilic coupling agent contains following component: aluminate coupling agent 25～30%, lipid acid 34～38% and tensio-active agent 9～14% by mass percentage.
Further, described aluminate coupling agent has following general formula:
In the formula, R
1And R
2Be independently-OCOR
4,-OSO
2R
5Or-OPO (OR
6)
2, R
4, R
5And R
6Be C independently
3～C
21Alkyl, C
3～C
21Cycloalkyl, C
2～C
21Thiazolinyl or by C
7～C
21The phenyl that alkyl replaces; R
3For having the organic amine compound of lone electron pair nitrogen-atoms;
Further, R
3Be primary octadecylamine, O-Phenylene Diamine, stearic amide, amine hydroxybenzene or erucicamide;
Further, R
4Be different heptyl, C
7～C
21Cycloalkyl, vinyl, 8-17 thiazolinyls or 12-two hendecene bases; R
5Be dodecylphenyl; R
6Be iso-octyl;
Further, described lipid acid is one or more in lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and the erucic acid;
Further, described tensio-active agent is one or more in glyceryl monostearate, Polyglycerine monostearate, sorbitol anhydride mono fatty acid ester, sorbitol anhydride mono-laurate, polyoxyethylene sorbitan monostearate and the polyoxyethylenesorbitan sorbitan monooleate.
2, the preparation method of described amphiphilic coupling agent, may further comprise the steps: in the inert organic solvents that accounts for amphiphilic coupling agent scheduled production mass percent 21～25%, add tri-alkoxy aluminium, stir and heat and make it to dissolve fully, add organic amine compound with lone electron pair nitrogen-atoms, adding and tri-alkoxy al mole ratio are 3: 1 lipid acid again, in temperature is 125～130 ℃ of stirring reactions 0.5～1.5 hour, low-boiling by-products is removed in underpressure distillation simultaneously, promptly gets the aluminate coupling agent that accounts for amphiphilic coupling agent scheduled production mass percent 25～30%; In the gained aluminate coupling agent, add the lipid acid that accounts for amphiphilic coupling agent scheduled production mass percent 34～38%, stirring makes it to dissolve fully, add the tensio-active agent that accounts for amphiphilic coupling agent scheduled production mass percent 9～14% again, in temperature is 115～120 ℃ of stirring reactions 1 hour, be cooled to room temperature, promptly get amphiphilic coupling agent.
Further, described inert organic solvents is selected from one or more in whiteruss, solvent oil, dimethylbenzene and the hexanaphthene;
Further, described tri-alkoxy aluminium is aluminium isopropoxide; Described organic amine compound with lone electron pair nitrogen-atoms is primary octadecylamine, O-Phenylene Diamine, stearic amide, amine hydroxybenzene or erucicamide; Described lipid acid is selected from one or more in lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and the erucic acid;
Further, described tensio-active agent is one or more in glyceryl monostearate, Polyglycerine monostearate, sorbitol anhydride mono fatty acid ester, sorbitol anhydride mono-laurate, polyoxyethylene sorbitan monostearate and the polyoxyethylenesorbitan sorbitan monooleate.
Beneficial effect of the present invention is:
The invention provides a kind of amphiphilic coupling agent, it contains the parents' group that is three-dimensional net structure, and the water-wet side of this parents' group can be strapped in the water molecules in the powder in the network on the one hand, and the water molecules thermal motion is restricted, and is difficult for overflowing from network; Can merge with water molecules on the other hand and form the swelling gelinite, by the fusion effect between physical crosslinking, chemically crosslinked and physical-chemical mixing crosslinked action increase powder and the resin matrix; Thereby the hydrophobic end of this parents' group can form chemical bonding with powder and carry out the multiple spot anchoring.
The present invention preferably has the aluminate coupling agent of above-mentioned general formula, and isopropoxy has good hydrolysis reaction activity, can with hydrophilic radical generation physics, chemistry or the physics chemical action of powder surface; Defined R
1And R
2Group has good stability to hydrolysis and can be by changing structure type, chain length and/or sterically hindered etc. the adjusting, to improve consistency and the reactive force between powder and the resin matrix; Defined R
3Group is the associativity that good ligand and number that can be by choice structure type or nitrogen-atoms etc. overcome or reduce powder.
The invention solves traditional coupling agent to a high-moisture or the unfavorable difficult problem of the powder-modified effect of high hydroxyl content, the amphiphilic coupling agent that is provided has the characteristics of direct modification high-moisture or high hydroxyl content powder, need not before modification powder to be carried out harsh oven dry handles, can simplify powder-modified production technique, shortened process, save investment, save manpower and energy consumption, reduce production costs, reduce environmental pollution, be applicable to that inorganic powder is (as water-ground limestone, light calcium carbonate, talcum powder, wollastonite, barite and kaolin etc.) and the dry method of organic powder (as wood powder and starch etc.) or wet-process modified, a plurality of factories result on trial shows to have good effect; The preparation method of the amphiphilic coupling agent that is provided is simple, is fit to large-scale industrialization production.
The using method of amphiphilic coupling agent of the present invention is simple, and during dry method modification, directly adding gets final product, and usage quantity is 0.1～1.0% of a powder quality, and the control drop temperature is 120 ℃; When wet-process modified, add to grind in the ripe slurry of powder and get final product, usage quantity is 0.1～1.0% of a powder quality.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, below the preferred embodiments of the present invention and effect thereof are described in detail.
Embodiment 1
In whiteruss 365g, add aluminum isopropylate 102g (0.5mol), stirring and heating dissolves aluminum isopropylate fully, add primary octadecylamine 20g, stir, be warming up to 110 ℃, add stearic acid 426g (1.5mol), 125～130 ℃ of stirring reactions of temperature control 50 minutes, Virahol and other low-boiling by-products are removed in underpressure distillation simultaneously, get aluminate coupling agent; In the gained aluminate coupling agent, add stearic acid 525g, stirring makes it to dissolve fully, add stearin 61g and sorbitol anhydride mono fatty acid ester 70g again, 115～120 ℃ of stirring reactions of temperature control 1 hour (making the abundant grafting of tensio-active agent and aluminate coupling agent), be cooled to room temperature, promptly get the amphiphilic coupling agent 1479g of the paste that is white in color, contain aluminate coupling agent 29.6% by mass percentage, lipid acid 36%, tensio-active agent 9%.
Embodiment 2
In solvent oil 158g, add aluminum isopropylate 61.2g (0.3mol), stirring and heating dissolves aluminum isopropylate fully, add erucicamide 12g, stir, be warming up to 110 ℃, add lauric acid 180g (0.9mol), 125～130 ℃ of stirring reactions of temperature control 60 minutes, Virahol and other low-boiling by-products are removed in underpressure distillation simultaneously, get aluminate coupling agent; In the gained aluminate coupling agent, add tetradecanoic acid 280g, stirring makes it to dissolve fully, add polyoxyethylene sorbitan monostearate 101g again, 115～120 ℃ of stirring reactions of temperature control 1 hour (making the abundant grafting of tensio-active agent and aluminate coupling agent), be cooled to room temperature, promptly get the amphiphilic coupling agent 738g of the paste that is white in color, contain aluminate coupling agent 29.6% by mass percentage, lipid acid 38%, tensio-active agent 13.7%.
Embodiment 3
In hexanaphthene 203g, add aluminum isopropylate 61.2g (0.3mol), stirring and heating dissolves aluminum isopropylate fully, add amine hydroxybenzene 10g, stir, be warming up to 110 ℃, add palmitinic acid 230g (0.9mol), 125～130 ℃ of stirring reactions of temperature control 65 minutes, Virahol and other low-boiling by-products are removed in underpressure distillation simultaneously, get aluminate coupling agent; In the gained aluminate coupling agent, add erucic acid 296g, stirring makes it to dissolve fully, add sorbitol anhydride mono-laurate 40g and Polyglycerine monostearate 61.57g again, 115～120 ℃ of stirring reactions of temperature control 1 hour (making the abundant grafting of tensio-active agent and aluminate coupling agent), be cooled to room temperature, promptly get the amphiphilic coupling agent 847.5g of the paste that is white in color, contain aluminate coupling agent 28% by mass percentage, lipid acid 34.9%, tensio-active agent 12%.
Embodiment 4
In whiteruss 384g, add aluminum isopropylate 81.6g (0.4mol), stirring and heating dissolves aluminum isopropylate fully, add O-Phenylene Diamine 20g, stir, be warming up to 110 ℃, add erucic acid 405.6g (1.2mol), 125～130 ℃ of stirring reactions of temperature control 50 minutes, Virahol and other low-boiling by-products are removed in underpressure distillation simultaneously, get aluminate coupling agent; In the gained aluminate coupling agent, add stearic acid 568g, stirring makes it to dissolve fully, add polyoxyethylene sorbitan monostearate 154g again, 115～120 ℃ of stirring reactions of temperature control 1 hour (making the abundant grafting of tensio-active agent and aluminate coupling agent), be cooled to room temperature, promptly get the amphiphilic coupling agent 1541g of the paste that is white in color, contain aluminate coupling agent 26.9% by mass percentage, lipid acid 36.9%, tensio-active agent 10%.
Application Example 1
Be properties-correcting agent with aluminate coupling agent XB-1, titanate coupling agent NDZ-105, silane resin acceptor kh-550 and embodiment 1 gained amphiphilic coupling agent respectively, the dry method modification water content is 10% 1250 order heavy calcium carbonates, the coupling agent consumption is 1% of a heavy calcium carbonate quality, and drop temperature is 120 ℃; With the modified heavy calcium carbonate powder with make film after polyvinyl chloride (PVC) mixes, observe the face outward appearance, and load and elongation at break detection are broken in sampling (wide 1mm * long 5mm * thick 0.05mm).
The results are shown in Table 1, compare with the film of aluminate coupling agent, titanate coupling agent or the preparation of silane coupler modified heavy calcium carbonate, film with the preparation of embodiment 1 gained amphiphilic coupling agent modified heavy calcium carbonate powder, it is broken load and has improved 20.9%, 19.1%, 24.8% respectively, elongation at break has improved 11.6%, 21.5%, 15.7% respectively, and surface smoothness is good.
Table 1 detected result
Application Example 2
Be properties-correcting agent with aluminate coupling agent XB-1, titanate coupling agent NDZ-105, silane resin acceptor kh-550 and embodiment 2 gained amphiphilic coupling agents respectively, the dry method modification water content is 5% starch, the coupling agent consumption is 1% of a starch quality, and drop temperature is 120 ℃; Prepare degradable master batch with treated starch, further make film again, observe the face outward appearance, and load is broken in sampling (wide 1mm * long 5mm * thick 0.05mm) and elongation at break detects.
The results are shown in Table 2, compare with film with aluminate coupling agent, titanate coupling agent or the preparation of silane coupler modified starch, film with the preparation of embodiment 2 gained amphiphilic coupling agent treated starches, it is broken load and has improved 15.8%, 25.7%, 17.9% respectively, elongation at break has improved 15.8%, 25.7%, 17.9% respectively, and surface smoothness is good.
Table 2 detected result
Application Example 3
Be properties-correcting agent with aluminate coupling agent XB-1, titanate coupling agent NDZ-105, silane resin acceptor kh-550 and embodiment 3 gained amphiphilic coupling agents respectively, the dry method modification water content is 10% wood powder (is to mix at 7: 3 according to mass ratio by Cortex Fraxini mandshuricae and poplar), the coupling agent consumption is 1% of a wood powder quality, and drop temperature is 120 ℃; Be mixed and made into wood floors with modified wood powder and PVC, observe toughness, wear resistance and the surface smoothness on floor.
The result shows that with the floor of embodiment 3 gained amphiphilic coupling agent modified wood powders preparation, its toughness, wear resistance and surface smoothness all are better than with other three kinds of floors that coupling agent modified wood powder is made.
Application Example 4
Be properties-correcting agent with aluminate coupling agent XB-1, titanate coupling agent NDZ-105, silane resin acceptor kh-550 and embodiment 4 gained amphiphilic coupling agents respectively, the dry method modification water content is 8% talcum powder, the coupling agent consumption is 1% of a talcum powder quality, and drop temperature is 120 ℃; Prepare transparent masterbatches with modified talc powder, further make film again, observe the face outward appearance, and load is broken in sampling (wide 1mm * long 5mm * thick 0.05mm) and elongation at break detects.
The results are shown in Table 3, compare with film with aluminate coupling agent, titanate coupling agent or the preparation of silane coupler modified talcum powder, film with the preparation of embodiment 4 gained amphiphilic coupling agent modified talc powders, it is broken load and has improved 13.8%, 12.8%, 22.2% respectively, elongation at break has improved 12.0%, 36.6%, 17.3% respectively, and surface smoothness and light transmission are good.
Table 3 detected result
From above-mentioned effect as can be seen, amphiphilic coupling agent of the present invention is the organic powder (as wood powder, starch etc.) of the inorganic powder of modification high-moisture (as heavy calcium carbonate, talcum powder etc.) and high hydroxyl content directly, surface smoothness with the derived product of its modified powder preparation is good, defects such as no scratches and brilliant point are broken physical indexs such as load and elongation at break and all are better than traditional aluminate coupling agent, titanate coupling agent and silane coupling agent.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (10)
1, amphiphilic coupling agent is characterized in that: contain following component by mass percentage: aluminate coupling agent 25～30%, lipid acid 34～38% and tensio-active agent 9～14%.
2, amphiphilic coupling agent according to claim 1 is characterized in that: described aluminate coupling agent has following general formula:
In the formula, R
1And R
2Be independently-OCOR
4,-OSO
2R
5Or-OPO (OR
6)
2, R
4, R
5And R
6Be C independently
3～C
21Alkyl, C
3～C
21Cycloalkyl, C
2～C
21Thiazolinyl or by C
7～C
21The phenyl that alkyl replaces; R
3For having the organic amine compound of lone electron pair nitrogen-atoms.
3, amphiphilic coupling agent according to claim 2 is characterized in that: R
3Be primary octadecylamine, O-Phenylene Diamine, stearic amide, amine hydroxybenzene or erucicamide.
4, amphiphilic coupling agent according to claim 2 is characterized in that: R
4Be different heptyl, C
7～C
21Cycloalkyl, vinyl, 8-17 thiazolinyls or 12-two hendecene bases; R
5Be dodecylphenyl; R
6Be iso-octyl.
5, amphiphilic coupling agent according to claim 1 is characterized in that: described lipid acid is one or more in lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and the erucic acid.
6, amphiphilic coupling agent according to claim 1 is characterized in that: described tensio-active agent is one or more in glyceryl monostearate, Polyglycerine monostearate, sorbitol anhydride mono fatty acid ester, sorbitol anhydride mono-laurate, polyoxyethylene sorbitan monostearate and the polyoxyethylenesorbitan sorbitan monooleate.
7, the preparation method of the described amphiphilic coupling agent of claim 1, it is characterized in that: may further comprise the steps: in the inert organic solvents that accounts for amphiphilic coupling agent scheduled production mass percent 21～25%, add tri-alkoxy aluminium, stir and heat and make it to dissolve fully, add organic amine compound with lone electron pair nitrogen-atoms, adding and tri-alkoxy al mole ratio are 3: 1 lipid acid again, in temperature is 125～130 ℃ of stirring reactions 0.5～1.5 hour, low-boiling by-products is removed in underpressure distillation simultaneously, promptly gets the aluminate coupling agent that accounts for amphiphilic coupling agent scheduled production mass percent 25～30%; In the gained aluminate coupling agent, add the lipid acid that accounts for amphiphilic coupling agent scheduled production mass percent 34～38%, stirring makes it to dissolve fully, add the tensio-active agent that accounts for amphiphilic coupling agent scheduled production mass percent 9～14% again, in temperature is 115～120 ℃ of stirring reactions 1 hour, be cooled to room temperature, promptly get amphiphilic coupling agent.
8, the preparation method of amphiphilic coupling agent according to claim 7 is characterized in that: described inert organic solvents is selected from one or more in whiteruss, solvent oil, dimethylbenzene and the hexanaphthene.
9, the preparation method of amphiphilic coupling agent according to claim 7 is characterized in that: described tri-alkoxy aluminium is aluminium isopropoxide; Described organic amine compound with lone electron pair nitrogen-atoms is primary octadecylamine, O-Phenylene Diamine, stearic amide, amine hydroxybenzene or erucicamide; Described lipid acid is selected from one or more in lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and the erucic acid.
10, the preparation method of amphiphilic coupling agent according to claim 7 is characterized in that: described tensio-active agent is one or more in glyceryl monostearate, Polyglycerine monostearate, sorbitol anhydride mono fatty acid ester, sorbitol anhydride mono-laurate, polyoxyethylene sorbitan monostearate and the polyoxyethylenesorbitan sorbitan monooleate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571019A (en) * | 2013-11-19 | 2014-02-12 | 芮城新泰纳米材料有限公司 | Nanometer calcium carbonate composite concentrated master batch and preparation method thereof |
| CN112442289A (en) * | 2020-11-10 | 2021-03-05 | 桂林桂广申巴粉体材料有限责任公司 | Modified talcum powder, and preparation method and application thereof |
| CN112980329A (en) * | 2021-02-26 | 2021-06-18 | 山东福源节能环保工程有限公司 | Flue polymer composite anticorrosive paint formula |
| CN115594993A (en) * | 2022-10-12 | 2023-01-13 | 江西广源化工有限责任公司（Cn） | Aluminate coupling agent and preparation method and application thereof |
| CN117624732A (en) * | 2023-12-19 | 2024-03-01 | 湖南理工学院 | Calcined kaolin modified particle with surface amphiphilicity and preparation method thereof |
Family Cites Families (3)
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| CN88101604A (en) * | 1988-03-22 | 1988-12-14 | 福建师范大学 | With the Al-system coupling agent is the novel filling master batch of properties-correcting agent |
| CN1181128C (en) * | 2002-09-27 | 2004-12-22 | 南风化工集团股份有限公司 | Polyolefin packing material and its production method |
| CN101503577B (en) * | 2009-02-24 | 2012-03-21 | 重庆市嘉世泰化工有限公司 | Grinding-aid coupling agent and preparation thereof |
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2009
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| CN103571019A (en) * | 2013-11-19 | 2014-02-12 | 芮城新泰纳米材料有限公司 | Nanometer calcium carbonate composite concentrated master batch and preparation method thereof |
| CN103571019B (en) * | 2013-11-19 | 2015-11-04 | 芮城新泰纳米材料有限公司 | Nano-calcium carbonate compound concentrates masterbatch and preparation method thereof |
| CN112442289A (en) * | 2020-11-10 | 2021-03-05 | 桂林桂广申巴粉体材料有限责任公司 | Modified talcum powder, and preparation method and application thereof |
| CN112442289B (en) * | 2020-11-10 | 2021-09-14 | 桂林桂广申巴粉体材料有限责任公司 | Modified talcum powder, and preparation method and application thereof |
| CN112980329A (en) * | 2021-02-26 | 2021-06-18 | 山东福源节能环保工程有限公司 | Flue polymer composite anticorrosive paint formula |
| CN115594993A (en) * | 2022-10-12 | 2023-01-13 | 江西广源化工有限责任公司（Cn） | Aluminate coupling agent and preparation method and application thereof |
| CN115594993B (en) * | 2022-10-12 | 2023-12-05 | 江西广源化工有限责任公司 | Aluminate coupling agent and preparation method and application thereof |
| CN117624732A (en) * | 2023-12-19 | 2024-03-01 | 湖南理工学院 | Calcined kaolin modified particle with surface amphiphilicity and preparation method thereof |
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